Hydrogen furnace system and method

ABSTRACT

Apparatus and operating methods are provided for controlled atmosphere furnace systems. In one possible embodiment, hydrogen is injected from a hydrogen source to an enclosure. The hydrogen is circulated within the enclosure from a gas inlet to a gas outlet. A temperature is raised within the enclosure to a predetermined threshold. Hydrogen is pumped from the gas outlet to the gas inlet with an electrochemical hydrogen pump. The electrochemical hydrogen pump has a first electrode in fluid communication with the gas outlet, and a second electrode in fluid communication with the gas inlet. An electrical potential is provided between the first and second electrodes, wherein the first electrode has a higher electrical potential with respect to zero than the second electrode. Various methods, features and system configurations are discussed.

CROSS REFERENCE TO RELATED APPLICATIONS Technical Field of the Invention

The present invention relates to apparatus and operating methods forfurnaces which utilize hydrogen and electrochemical hydrogen separationsystems. Various methods, features and system configurations arediscussed.

BACKGROUND

Various uses are known for controlled atmosphere furnaces. For example,as part of a manufacturing process, it may be desirable to condition amaterial or article of manufacture by heating it in the presence ofhydrogen. Such systems are sometimes referred to as hydrogen furnaces.In such applications, there is a need for apparatus and methods forproviding and processing the hydrogen, as well as for operating anintegrated system.

A variety of hydrogen-based electrochemical fuel cell technologies areknown, wherein electrical power is produced by reacting a fuel such ashydrogen in an electrochemical cell to produce a flow of electronsacross the cell, thus providing an electrical current. For example, infuel cells utilizing proton exchange membrane technology, anelectrically non-conducting proton exchange membrane is typicallysandwiched between two catalyzed electrodes. One of the electrodes,typically referred to as the anode, is contacted with hydrogen. Thecatalyst at the anode serves to divide the hydrogen molecules into theirrespective protons and electrons. Each hydrogen molecule produces twoprotons which pass through the membrane to the other electrode,typically referred to as the cathode. The protons at the cathode reactwith oxygen to form water, and the residual electrons at the anodetravel through an electrically conductive path around the membrane toproduce an electrical current from anode to cathode. The technology isclosely analogous to conventional battery technology.

Electrochemical cells can also be used to selectively transfer (or“pump”) hydrogen from one side of the cell to another. For example, in acell utilizing a proton exchange membrane, the membrane is sandwichedbetween a first electrode (anode) and a second electrode (cathode), agas containing hydrogen is placed at the first electrode, and anelectric potential is placed between the first and second electrodes,the potential at the first electrode with respect to ground (or “zero”)being greater than the potential at the second electrode with respect toground. Each hydrogen molecule reacted at the first electrode producestwo protons which pass through the membrane to the second electrode ofthe cell, where they are rejoined by two electrons to form a hydrogenmolecule (sometimes referred to as “evolving hydrogen” at theelectrode).

Electrochemical cells used in this manner are sometimes referred to ashydrogen pumps. In addition to providing controlled transfer of hydrogenacross the cell, hydrogen pumps can also be used to separate hydrogenfrom gas mixtures containing other components. Where the hydrogen ispumped into a confined space, such cells can be used to compress thehydrogen, at very high pressures in some cases.

There is a continuing need for apparatus, methods and applicationsrelating to hydrogen furnaces.

SUMMARY OF THE INVENTION

Apparatus and operating methods are provided for controlled atmospherefurnace systems. In one possible embodiment, hydrogen is injected from ahydrogen source to an enclosure. The hydrogen is circulated within theenclosure from a gas inlet to a gas outlet. A temperature can be raisedwithin the enclosure to a predetermined threshold. Hydrogen can beprocessed, routed, and/or purified in the system using anelectrochemical hydrogen pump. The electrochemical hydrogen pump has afirst electrode in fluid communication with the gas outlet, and a secondelectrode in fluid communication with the gas inlet. An electricalpotential is provided between the first and second electrodes, whereinthe first electrode has a higher electrical potential with respect tozero than the second electrode. Various aspects and features of theinvention will be apparent from the following Detailed Description andfrom the Claims.

DETAILED DESCRIPTION OF THE INVENTION

It will be appreciated that the apparatus, methods, and applications ofthe invention can include any of the features described herein, eitheralone or in combination.

In one embodiment of the present invention, a method is provided foroperating an integrated controlled atmosphere furnace system, includingat least the following steps: injecting hydrogen from a hydrogen sourceto an enclosure; circulating hydrogen within the enclosure from a gasinlet to a gas outlet; raising a temperature within the enclosure to apredetermined threshold; pumping hydrogen from the gas outlet to the gasinlet with an electrochemical hydrogen pump, wherein the electrochemicalhydrogen pump has a first electrode in fluid communication with the gasoutlet, and wherein the electrochemical hydrogen pump has a secondelectrode in fluid communication with the gas inlet; providing anelectrical potential between the first and second electrodes, whereinthe first electrode has a higher electrical potential with respect tozero than the second electrode; and using a second sensor to measurehydrogen downstream from the gas outlet.

The enclosure serves as an oven (also sometimes referred to as afurnace) into which materials or articles of manufacture can be placed.In some embodiments, a conveyor system can transport materials throughthe enclosure to achieve a desired residence time within the enclosure.Examples of such furnaces include pusher furnaces, tunnel kilns, rotarycalciners, or the like.

The hydrogen source can be a storage tank, such as a pressure vessel, ormore generally it can be any source of hydrogen, including gaseoushydrogen and vaporized liquid hydrogen. In some embodiments, systems maybe provided with multiple means of supplying hydrogen to the enclosure(e.g., from the hydrogen source, from the electrochemical cell outlet,etc.). For example, on start up, a hydrogen pressure vessel can be usedto charge the atmosphere of the enclosure with a desired amount ofhydrogen. In this context, the “atmosphere of the enclosure” refers tothe body of gas inside the enclosure. The atmosphere outside theenclosure may be referred to as ambient or ambient atmosphere in somecases.

During operation of the system, the electrochemical hydrogen pump can beused to recover and recirculate the hydrogen in the enclosure, in somecases to maintain a desired level of hydrogen in the enclosure. Forexample, in a system utilizing a conveyor passing through the enclosure,the electrochemical hydrogen pump can remove hydrogen from the enclosureatmosphere at the conveyor outlet or any other point to prevent thehydrogen from being vented to ambient where the conveyor exits theenclosure. Similarly, in furnace systems where the furnace enclosure issealed during use and then opened to allow removal of a material orarticle from the furnace when conditioning is complete, theelectrochemical hydrogen pump can serve to capture any hydrogen that maybe vented to the atmosphere outside the enclosure when the enclosure isopened. It will be appreciated that as the cell is maintained with avoltage across it, essentially any hydrogen that comes in contact withthe first electrode will be pumped to the second electrode.

As a part of the electrochemical pumping process, the electrochemicalhydrogen pump also serves to purify the hydrogen in the enclosure. Insome embodiments, the gas inside the enclosure can be purified by theelectrochemical pump by exhausting it from the enclosure, removinghydrogen from it, and injecting the pumped hydrogen into fresh gas thatis introduced into the enclosure. As examples, the fresh gas can behydrogen, air, nitrogen, or other gases suited for a particularapplication. It will also be appreciated that some of the hydrogen maybe consumed or reacted inside the system, for example in reaction withthe material or article being heated.

In general, any opening through which hydrogen can flow from theenclosure is referred to as a gas outlet. Similarly, any opening throughwhich hydrogen can flow into the enclosure is referred to as a gasinlet. In this context, circulation of hydrogen from the gas inlet tothe gas outlet refers to any flow of hydrogen into and/or out of theenclosure.

In some embodiments, the electrochemical hydrogen pump can also be usedto control hydrogen flow from the hydrogen source to the enclosure. Forexample, the pressure developed at the outlet of the electrochemicalhydrogen pump can be used to actuate a check valve leading to theenclosure. In some embodiments, the electrochemical hydrogen pump canalso be used to supply hydrogen to the hydrogen source. For example,recirculated hydrogen from the enclosure can be stored in a pressurevessel. It will be appreciated that electrochemical hydrogen pumps canbe used to generate substantial outlet pressures that can be variedaccording to the needs of a particular system configuration. Thus, insome embodiments, the step of pumping hydrogen from the gas outlet tothe gas inlet can include injecting hydrogen from the electrochemicalhydrogen pump into the hydrogen source.

Systems under the present invention can utilize any suitable means forcontrolling the temperature inside the enclosure. For example, anelectric heating element or combustion process can be used to raise thetemperature of the atmosphere inside the enclosure. In some embodiments,hydrogen can be combusted to provide the heat. It may also be necessaryto prevent combustion of hydrogen in the enclosure atmosphere. Forexample, the amount of oxygen in the enclosure may be limited, either byflushing the atmosphere with hydrogen, or by injecting an inert gas intothe enclosure atmosphere such as nitrogen. In some embodiments, systemsmay thus include an inert gas source adapted to flow inert gas into theenclosure. In some embodiments, an oxygen sensor can be used to detectoxygen in the enclosure atmosphere. As an example, such a sensor can becoupled to a controller configured to increase a flow of hydrogen and/orinert gas through the enclosure to maintain the oxygen concentration inthe enclosure below a predetermined threshold.

The electrochemical hydrogen pump can be any electrochemical cellsuitable for electrochemically pumping hydrogen. As an example, PEM(proton exchange membrane)-based cells can be used, where the protonexchange membrane can be any of various known materials suitable fortransporting protons (Polybenzimidazole (PBI), Nafion®, PEEK, etc.). Theproton conductor may also include solid state proton conductingmaterials such as Calcium Hydrogen Phosphate. In the present invention,while reference is generally made to individual cells, it will beappreciated that such cells can form individual units within stacks ofcells. The invention covers stack configurations as well as individualcell configurations.

In some embodiments of methods under the present invention, the step ofinjecting hydrogen from the hydrogen source to the enclosure isperformed in response to a signal from a first sensor adapted to measurehydrogen within the enclosure. For example, a controller can be used toactuate the pump as needed to maintain a desired concentration ofhydrogen in the enclosure.

In some instances, the electrochemical pump can be operated in a“pump-on-demand” mode, e.g., using a fixed applied voltage to drive anyhydrogen across the separator which comes into contact with it, whichwill generate a current proportional to the amount of hydrogen present.The voltage drop or the generated current in amperes can act in itselfas a “sensor” and be correlated to changes associated with the pump orthe furnace, such as hydrogen concentration, hydrogen flow, etc. Inother embodiments, a passive “on demand” system is provided where avoltage is maintained across the electrochemical hydrogen pumpsufficient to recirculate hydrogen as it comes into contact with thecell. It may thus be desirable to maintain the electrical potentialbetween the first and second electrodes of the cell above apredetermined threshold according to the operating characteristics ofthe cell (e.g., 0.3 volts, 0.7 volts, 1.0 volts, etc.).

In some embodiments, methods under the present invention may include thestep of oxidizing an effluent gas from the furnace gas outlet. In someembodiments, this step may be performed when a signal from the secondsensor measuring hydrogen at the gas outlet indicates that a hydrogenlevel of the effluent gas is above a predetermined threshold. Thus, thesystem can be configured to ensure that hydrogen is not vented to theatmosphere outside the enclosure.

In some embodiments, methods under the present invention may include thestep of humidifying an effluent gas from the gas outlet at a locationthat is upstream from the first electrode of the electrochemicalhydrogen pump. It will be appreciated that in some cases it can bedesirable to operate an electrochemical cell in a humidified state.Thus, the gas that is contacted with the cell can be humidified. It willalso be appreciated that some electrochemical cells operate moreefficiently at elevated temperatures. For example, with PBI-based cells,operation may be desired at about 100 C or other temperatures accordingto the particular PBI based membrane that is utilized. In someembodiments, the systems under the present invention can thermallyintegrate the enclosure with the cell to provide the cell with suitableheat for operating at elevated temperatures. For example, the cell canbe located or partially located within the enclosure. Such systems mayalso include a mechanism such as a fan or coolant circuit for coolingthe cell. Liquid cooling methods may also be incorporated as potentialsub-systems to the systems described herein.

In some embodiments, a controller can be coupled to a network of sensorsto maintain a desired hydrogen concentration in the enclosure. As anexample, the step of injecting hydrogen from the hydrogen source to theenclosure can be performed when a hydrogen level within the enclosure isbelow a predetermined threshold, and the step of pumping hydrogen fromthe gas outlet to the gas inlet can be performed when a hydrogen leveldownstream from the gas outlet is above a predetermined threshold.

In some embodiments, systems and associated methods under the presentinvention can include utilizing various known hydrogen separationmethods to filter hydrogen from the electrochemical hydrogen pumpeffluent to the gas inlet. For example, such separation methods caninclude palladium membranes or other polymer or ceramic membranessuitable for filtering hydrogen. In particular, palladium membranes area well known means of filtering hydrogen from a source gas. As anexample, a palladium membrane can be positioned in fluid communicationbetween the second electrode of the electrochemical hydrogen pump andthe gas inlet. As known in the art, in some cases it may be desirable toheat the palladium membrane to a desired operating temperature, suchtemperature chosen according to the operating characteristics of theparticular palladium membrane system utilized.

In another embodiment, the invention provides a controlled atmospherefurnace system. The system includes a gas inlet and a gas outlet, and anelectrochemical hydrogen pump. The electrochemical hydrogen pump has afirst electrode in fluid communication with the gas outlet, and a secondelectrode in fluid communication with the gas inlet. The system alsoincludes a power supply adapted to maintain an electrical potentialbetween the first and second electrodes, wherein the first electrode hasa higher electrical potential with respect to zero than the secondelectrode. A hydrogen source is adapted to flow hydrogen into theenclosure. A first sensor is adapted to measure hydrogen within theenclosure, and a second sensor is adapted to measure hydrogen downstreamfrom the gas outlet. A heater is adapted within the system to raise aninternal temperature of the enclosure.

A controller is configured to restrict a flow of hydrogen from thehydrogen source to the enclosure in response to a signal from the firstsensor when a hydrogen level at the first sensor is below apredetermined threshold. The controller can also be adapted to energizethe electrochemical hydrogen pump to flow hydrogen from the gas outletto the gas inlet in response to a signal from the second sensor when ahydrogen level at the second sensor is above a predetermined threshold.The controller can also be adapted to modulate a flow of inert gas intothe enclosure to maintain an oxygen level in the enclosure below apredetermined threshold.

In some embodiments, systems under the present invention can alsoinclude a vent in fluid communication between the gas outlet and anatmosphere external to the system, and an oxidizer adapted to removehydrogen from an effluent gas flowed through the vent to the atmosphere.As examples, the oxidizer can be a flame, electrical heating element, orarrangement similar to an automotive catalytic converter.

The inventive concepts discussed in the claims build on traditionalelectrochemical cells technologies that are well known in the art. Asexamples, various suitable designs and operating methods that can beused as a base to implement the present invention are described in theteachings of U.S. Pat. Nos. 4,620,914; 6,280,865; 7,132,182 andpublished U.S. patent application Ser. Nos. 10/478,852, 11/696,179,11/737,730, 11/737,733, 11/737,737, and 11/743,612 which are each herebyincorporated by reference in their entirety.

While the invention has been shown or described in only some of itsforms, it should be apparent to those skilled in the art that it is notso limited, but is susceptible to various changes without departing fromthe scope of the invention.

1-17. (canceled)
 18. A method of operating an integrated controlledatmosphere furnace system comprising: providing a controlled atmospherefurnace to condition a material or an article of manufacture by heatingin the presence of hydrogen, the controlled atmosphere furnace has afurnace gas inlet and a furnace gas outlet, said furnace having aconveyor therethrough; injecting hydrogen from a hydrogen source to thecontrolled atmosphere furnace through the furnace gas inlet; circulatinghydrogen within the controlled atmosphere furnace from the furnace gasinlet to the furnace gas outlet; pumping hydrogen from the furnace gasoutlet to the furnace gas inlet with an electrochemical hydrogen pump,the hydrogen entering into the furnace gas inlet from theelectrochemical hydrogen pump consists of hydrogen, the electrochemicalhydrogen pump being outside the controlled atmosphere furnace, theelectrochemical hydrogen pump has a first electrode in fluidcommunication with the furnace gas outlet and has a second electrode influid communication with the furnace gas inlet; and providing anelectrical potential between the first and second electrodes, the firstelectrode has a higher electrical potential with respect to zero thanthe second electrode.
 19. A method of operating an integrated controlledatmosphere furnace system comprising: providing a controlled atmospherefurnace to condition a material or an article of manufacture by heatingin the presence of hydrogen, the controlled atmosphere furnace has afurnace gas inlet and a furnace gas outlet, said furnace being sealedduring use; injecting hydrogen from a hydrogen source to the controlledatmosphere furnace through the furnace gas inlet; circulating hydrogenwithin the controlled atmosphere furnace from the furnace gas inlet tothe furnace gas outlet; pumping hydrogen from the furnace gas outlet tothe furnace gas inlet with an electrochemical hydrogen pump, thehydrogen entering into the furnace gas inlet from the electrochemicalhydrogen pump consists of hydrogen, the electrochemical hydrogen pumpbeing outside the controlled atmosphere furnace, the electrochemicalhydrogen pump has a first electrode in fluid communication with thefurnace gas outlet and has a second electrode in fluid communicationwith the furnace gas inlet; and providing an electrical potentialbetween the first and second electrodes, the first electrode has ahigher electrical potential with respect to zero than the secondelectrode.
 20. A method of operating an integrated controlled atmospherefurnace system comprising: providing a controlled atmosphere furnace tocondition a material or an article of manufacture by heating in thepresence of hydrogen, the controlled atmosphere furnace has a furnacegas inlet and a furnace gas outlet; injecting hydrogen from a hydrogensource to the controlled atmosphere furnace through the furnace gasinlet; circulating hydrogen within the controlled atmosphere furnacefrom the furnace gas inlet to the furnace gas outlet; pumping hydrogenfrom the furnace gas outlet to the furnace gas inlet with anelectrochemical hydrogen pump, the hydrogen entering into the furnacegas inlet from the electrochemical hydrogen pump consists of hydrogen,the electrochemical hydrogen pump being outside the controlledatmosphere furnace, the electrochemical hydrogen pump has a firstelectrode in fluid communication with the furnace gas outlet and has asecond electrode in fluid communication with the furnace gas inlet; andproviding an electrical potential between the first and secondelectrodes, the first electrode has a higher electrical potential withrespect to zero than the second electrode, the electrochemical pumpincluding a proton exchange membrane.
 21. The method according to claim20 wherein the proton exchange membrane being made of a materialselected from selected from the group consisting of: polybenzimidazole,perfluorosulfonic acid, PEEK, and solid state proton conductingmaterial.
 22. The method according to claim 21 wherein the solid stateproton conducting material being calcium hydrogen phosphate.
 23. Amethod of operating an integrated controlled atmosphere furnace systemcomprising: providing a controlled atmosphere furnace to condition amaterial or an article of manufacture by heating in the presence ofhydrogen, the controlled atmosphere furnace has a furnace gas inlet anda furnace gas outlet; injecting hydrogen from a hydrogen source to thecontrolled atmosphere furnace through the furnace gas inlet; circulatinghydrogen within the controlled atmosphere furnace from the furnace gasinlet to the furnace gas outlet; pumping hydrogen from the furnace gasoutlet to the furnace gas inlet with an electrochemical hydrogen pump,the hydrogen entering into the furnace gas inlet from theelectrochemical hydrogen pump consists of hydrogen, the electrochemicalhydrogen pump being outside the controlled atmosphere furnace, theelectrochemical hydrogen pump has a first electrode in fluidcommunication with the furnace gas outlet and has a second electrode influid communication with the furnace gas inlet; and providing anelectrical potential between the first and second electrodes, the firstelectrode has a higher electrical potential with respect to zero thanthe second electrode; and controlling hydrogen content within thecontrolled atmosphere furnace via a controller connected to a network ofsensors.
 24. A method of operating an integrated controlled atmospherefurnace system comprising: providing a controlled atmosphere furnace tocondition a material or an article of manufacture by heating in thepresence of hydrogen, the controlled atmosphere furnace has a furnacegas inlet and a furnace gas outlet; injecting hydrogen from a hydrogensource to the controlled atmosphere furnace through the furnace gasinlet; circulating hydrogen within the controlled atmosphere furnacefrom the furnace gas inlet to the furnace gas outlet; pumping hydrogenfrom the furnace gas outlet to the furnace gas inlet with anelectrochemical hydrogen pump, the hydrogen entering into the furnacegas inlet from the electrochemical hydrogen pump consists of hydrogen,the electrochemical hydrogen pump being outside the controlledatmosphere furnace, the electrochemical hydrogen pump has a firstelectrode in fluid communication with the furnace gas outlet and has asecond electrode in fluid communication with the furnace gas inlet; andproviding an electrical potential between the first and secondelectrodes, the first electrode has a higher electrical potential withrespect to zero than the second electrode; and filtering hydrogen with afilter located between the electrochemical pump and the furnace gasinlet.
 25. The method according to claim 24 wherein the filter being amembrane filter.
 26. The method according to claim 25 wherein themembrane filter being made of a material selected from the groupconsisting of palladium, polymer or ceramic.